Electrically conductive hybrid membrane, making method thereof, secondary battery and electronic device comprising the same

ABSTRACT

An electrically conductive hybrid membrane, including a solid membrane substrate including a curable material; and electrically conductive particle disposed on the solid membrane substrate, wherein the solid membrane substrate has an elastic modulus of about 10 MPa to about 1000 MPa, and the electrically conductive particle is exposed on both sides of the solid membrane substrate.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of U.S. patent application Ser. No.16/734,549, filed on Jan. 6, 2020, and claims priority to and thebenefit of Korean Patent Application No. 10-2019-0007795 filed in theKorean Intellectual Property Office on Jan. 21, 2019, and all thebenefits accruing therefrom under 35 U.S.C. § 119, the entire contentsof which are incorporated herein by reference.

BACKGROUND 1. Field

An electrically conductive hybrid membrane, a making method thereof, anda secondary battery and an electronic device including the same aredisclosed.

2. Description of the Related Art

According to the growing desire for a secondary battery providing ahigh-capacity and a high power, a variety of secondary batteries such asa lithium battery (LiB) has been researched. An all-solid-state batteryand a secondary battery including metal-oxygen, or metal-air may have ahigher theoretical specific energy 3 to 5 times of that of a lithium ionbattery, due to the atomic density of a low atomic number element, suchas lithium or the like.

In a positive electrode of the battery as above, a metal atom (e.g.,lithium atom) is oxidized to form an ion (e.g., lithium ion) and anelectron, and the produced ion is moved to a negative electrode by anelectrolyte, so as to be reacted with gas.

An electrically conductive hybrid membrane passing the ion but notpermeating moisture or the like may be disposed between the electrolyteand the positive electrode. The electrically conductive hybrid membranemay block the exchange of other materials except ions between thepositive electrode and the negative electrode, thus it may prevent thatother materials are transported to a positive electrode and/or anegative electrode to occur a side reaction.

An anisotropic conductive film is widely used as a connection materialbetween a liquid crystal panel and an organic light emitting diodes(OLED) panel, and a driver IC in an electronic device such as a liquidcrystal display and an organic light emitting display. The anisotropicconductive film is electrically insulated from adjacent components, andfunctions to electrically connect the connected panel to the driver IC.

It is desirable for the membrane having electrical conductivity (ionand/or electron conductivity) to have high conductivity for ions and/orelectrons, workability for being processed to have a large area,mechanical flexibility, and a barrier property for reactive materialsuch as water, oxygen, or carbon dioxide.

SUMMARY

An electrically conductive hybrid membrane having improved workability,flexibility, and barrier properties is provided.

In addition, a method of making the electrically conductive hybridmembrane by a simple method is provided.

A secondary battery capable of reducing a side reaction between an ionconductive membrane, and an electrode, and an electronic device capableof connecting internal constituent elements by including theelectrically conductive hybrid membrane are provided.

An electrically conductive hybrid membrane includes: a solid membranesubstrate including a curable material; and an electrically conductiveparticle disposed on the solid membrane substrate, wherein the solidmembrane substrate has an elastic modulus of about 10 megaPascals (MPa)to about 1000 MPa, and the electrically conductive particle is exposedon both sides of the solid membrane substrate.

The solid membrane substrate may have an insulating property.

The curable material may include one or more of a thermosettingmaterial, an ultraviolet (UV) curable material, and a moisture curablematerial.

The curable material may have tackiness.

The conductive particles may be arranged in hexagonal shape.

The curable material may include an acryl-based compound, an epoxy-basedcompound, a urethane-based compound, a phenol-based compound, or acombination thereof.

A thickness of the solid membrane substrate may be less than or equal toa diameter of the conductive particles.

The conductive particles may include ion conductive particles, electronconductive particles, or a combination thereof.

The ion conductive particles may conduct at least one ion of a lithiumion, a sodium ion, a proton, a potassium ion, an iron ion, a zinc ion, amagnesium ion, and a potassium ion.

The ion conductive particle may have an ion conductivity of about 1×10⁻⁵S/cm to about 1×10⁻³ S/cm.

The ion conductive particle may include at least one of ZrO₂, AlO₃, anda compound represented by Chemical Formula 1 to Chemical Formula 4.

Li₃La_((2/3-x))TiO₃  Chemical Formula 1

Li_(y)La₃M¹ ₂O₁₂  Chemical Formula 2

Li_((2+2z))Zn_((1−z))GeO₄  Chemical Formula 3

Li_(w)M² ₂(PO₄)₃  Chemical Formula 4

In Chemical Formula 1 to Chemical Formula 4,

M¹ is at least one element of zirconium (Zr), niobium (Nb), tantalum(Ta), antimony (Sb), and bismuth (Bi),

M² is at least one element of Aluminum (Al), germanium (Ge), titanium(Ti), hafnium (Hf), and zirconium (Zr),

0≤w≤2, 0≤x≤2/3, 5≤y≤7, and

0≤z<1.

The electron conductive particle may include an elastomer and a metallayer disposed on the surface of the elastomer.

The elastomer may include a polystyrene-based compound, an epoxy-basedcompound, a polyimide-based compound, a phenol-based compound, or acombination thereof.

The metal layer may include gold (Au), silver (Ag), nickel (Ni),palladium (Pd), copper (Cu), or a combination thereof.

The metal layer may include two or more layers, and the two or morelayers may include different metals.

A method of making the electrically conductive hybrid membrane includes:disposing the electrically conductive particle on the membranesubstrate-forming layer, pressing the membrane substrate-forming layerand the electrically conductive particle, and curing the membranesubstrate-forming layer to make the electrically conductive hybridmembrane.

The pressing may be performed at a temperature higher than roomtemperature.

The pressing may be performed at a pressure of about 1 MPa to about 100MPa and at a temperature of about 50° C. to about 300° C.

Before the curing, the elastic modulus of the pressed membranesubstrate-forming layer may be less than or equal to about 100 kPa.

Before the pressing, a peel strength of the membrane substrate-forminglayer may be greater than or equal to about 0.05 N/25 mm.

The curing may include at least one of an ultraviolet (UV) curingprocess, a heat curing process, and a moisture curing process.

When a thickness of the membrane substrate-forming layer beforedisposing of the electrically conductive particles is referred to as tand a diameter of the conductive particles is referred to as D, t and Dmay satisfy the relationship of Equation 1.

t≤0.4×D  Equation 1

A secondary battery according includes a positive electrode; and anegative electrode; and the electrically conductive hybrid membranedisposed between the positive electrode and the negative electrode.

An electronic device includes the electrically conductive hybridmembrane.

The electrically conductive hybrid membrane may have improvedworkability, flexibility, ion conductivity, and barrier properties.Also, since the electrically conductive hybrid membrane may be made by arelatively simple method, mass productivity of the electricallyconductive hybrid membrane may be provided.

The secondary battery including the electrically conductive hybridmembrane may have improved ion conductivity, and a side reaction of theelectrode is reduced, which may lead to improved efficiency andcycle-life.

An electronic device including the electrically conductive hybridmembrane may have improved electrical conductivity between the connectedpanel and the driver integrated circuit (IC).

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other advantages and features of this disclosure willbecome more apparent by describing in further detail exemplaryembodiments thereof with reference to the accompanying drawings, inwhich:

FIG. 1 is a schematic view illustrating an exemplary embodiment of anelectrically conductive hybrid membrane:

FIG. 2 is a top plan view of an electrically conductive hybrid membraneaccording to an exemplary embodiment, viewed from either side of bothsides of the membrane;

FIG. 3 is a flow diagram of a process of making an electricallyconductive hybrid membrane according to an exemplary embodiment;

FIG. 4 is a schematic view showing electron conductive particlesdisposed to have the densest structure in the membrane substrate-forminglayer;

FIG. 5 is a graph of film thickness (micrometers, μm) versus particlediameter (micrometers, μm) showing the surface exposure of electronconductive particles in an electrically conductive hybrid membraneaccording to an embodiment, together with a relationship of an electronconductive particle diameter and the thickness of the membranesubstrate-forming layer before pressing.

FIG. 6 is a schematic view showing a secondary battery including anelectrically conductive hybrid membrane according to an exemplaryembodiment.

FIG. 7 is a schematic view illustrating an electronic device includingan electrically conductive hybrid membrane according to an exemplaryembodiment.

FIG. 8 is a scanning electron microscope (“SEM”) image showing the lowersurface of the electrically conductive hybrid membrane according toComparative Example 4.

FIGS. 9 and 10 are SEM images showing the upper surface (FIG. 9 ) andthe lower surface (FIG. 10 ) of the electrically conductive hybridmembrane according to Example 13.

FIGS. 11 and 12 are SEM images showing the upper surface (FIG. 11 ) andthe lower surface (FIG. 12 ) of the electrically conductive hybridmembrane according to Comparative Example 14.

DETAILED DESCRIPTION

Example embodiments of the present disclosure will hereinafter bedescribed in detail, and may be easily performed by a person having anordinary skill in the related art. However, this disclosure may beembodied in many different forms, and is not to be construed as limitedto the example embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc.,are exaggerated for clarity. Like reference numerals designate likeelements throughout the specification. It will be understood that whenan element such as a layer, film, region, or substrate is referred to asbeing “on” another element, it can be directly on the other element orintervening elements may also be present. In contrast, when an elementis referred to as being “directly on” another element, there are nointervening elements present.

It will be understood that, although the terms “first,” “second,”“third” etc. may be used herein to describe various elements,components, regions, layers and/or sections, these elements, components,regions, layers and/or sections should not be limited by these terms.These terms are only used to distinguish one element, component, region,layer or section from another element, component, region, layer orsection. Thus, “a first element,” “component,” “region,” “layer” or“section” discussed below could be termed a second element, component,region, layer or section without departing from the teachings herein.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. “At least one” is not to be construed as limiting “a” or“an.” “Or” means “and/or.” As used herein, the term “and/or” includesany and all combinations of one or more of the associated listed items.It will be further understood that the terms “comprises” and/or“comprising,” or “includes” and/or “including” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components, and/orgroups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±30%, 20%, 10% or 5% of the stated value.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this disclosure belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

Exemplary embodiments are described herein with reference to crosssection illustrations that are schematic illustrations of idealizedembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, embodiments described herein should not beconstrued as limited to the particular shapes of regions as illustratedherein but are to include deviations in shapes that result, for example,from manufacturing. For example, a region illustrated or described asflat may, typically, have rough and/or nonlinear features. Moreover,sharp angles that are illustrated may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the precise shape of a region and are notintended to limit the scope of the present claims.

As used herein, for a particle diameter of a particle in the presentdisclosure, although it may be numerized by a measurement to show anaverage size of a group, the generally used method includes a modediameter showing the maximum value of the distribution, a mediandiameter corresponding to the center value of integral distributioncurve, a variety of average diameters (numeral average, length average,area average, mass average, volume average), and the like. Unlessparticularly mentioning otherwise, an average particle diameter, or aparticle diameter, means a number average diameter in the presentdisclosure, and it is obtained by measuring D50 (particle diameter at aposition of distribution rate of 50%).

As used herein, electrical conductivity means a property in which acarrier having a charge moves so that a current flows between twocontacted constituent elements. Examples of the carrier include anelectron and an ion.

In the secondary battery and/or the electronic device, an electricallyconductive membrane for selectively conducting only a selected carrier(e.g., an ion such as a lithium ion or an electron) desirably providessuitable workability so it can be processed into a large area, hassuitable mechanical flexibility, high conductivity for the carrier, andbarrier properties to a reactive material such as water, oxygen, carbondioxide and the like.

However, there is no current material satisfying all the propertiesamong the available materials used for the electrically conductivemembrane. The available materials may include an organic gel, organicpolymer, inorganic non-oxide, ceramic glass, and the like.

For example, the organic gel has a weak mechanical strength and isvulnerable to gas and does not provide suitable electrical conductivity.The organic polymer seems to have excellent mechanical strength andflexibility and also has excellent barrier properties to gas, but doesnot provide suitable electrical conductivity. The inorganic non-oxideseems to have excellent electrical conductivity but does not providesuitable barrier properties since it has hygroscopicity and is reactivewith oxygen or the like. The ceramic glass has excellent electricalconductivity but has low mechanical strength and flexibility due to itsbrittleness, and it is difficult to be produced in a large area unlessincreasing the thickness.

As a substitute of the available materials, an organic/inorganic ororganic/inorganic/metal hybrid electrically conductive membrane has beensuggested. The organic/inorganic hybrid electrically conductive membraneprovides thermal stability and electrical conductivity through aninorganic or inorganic/metal hybrid electrically conductive material andprovides workability, flexibility, and other mechanical propertiesthrough an organic polymer.

However, the organic/inorganic or organic/inorganic/metal hybridelectrically conductive membrane applies a wet process. Thus, it isdifficult to ensure a mass production, since carrying out processes,such as etching the remaining organic polymer region and removing thesame after coating the organic polymer, can be difficult.

In order to improve this, it may be suggested that the inorganic orinorganic/metal hybrid electrically conductive material is disposed andthe organic polymer is coated under a vacuum, and a grid is disposedduring the drying process, but the organic polymer may be insufficientlypermeated under the grid, and it may cover the electrically conductivematerial. Thus, it is difficult to control the entire processconditions, therefore, it is not suitable for the mass production.

Also, another improving way may be considered that the conductivematerial is disposed on a thermoplastic organic polymer, and the bothsurfaces thereof are pressed, but the thermoplastic organic polymer istoo flexible to be peeled off after the pressing, and the inside and/orsurface defects of the membrane may occur.

Accordingly, there is increasing need for an electrically conductivehybrid membrane having excellent workability, flexibility, and barrierproperties and capable of being produced by the simple method to providea mass productivity.

An embodiment may provide electrically conductive hybrid membrane havingmass productivity since it is simply produced without complicatedprocess conditions comparing to an alternative process, and also havingall of workability, flexibility, and barrier properties, and a method ofmaking the same.

Hereinafter, a structure of an electrically conductive hybrid membraneaccording to an embodiment is further described.

FIG. 1 is a schematic view of an electrically conductive hybrid membraneaccording to an embodiment.

Referring to FIG. 1 , an electrically conductive hybrid membrane 10according to an embodiment includes a solid membrane substrate 110including a curable material and conductive particles 120 disposed onthe solid membrane substrate 110.

In an embodiment, the conductive particles 120 may be respectivelyexposed from both sides of the solid membrane substrate 110. In otherwords, the conductive particles 120 may be respectively exposed fromboth opposing surfaces (referring to FIG. 1 , upper and lower surfacesof membrane substrate) of the solid membrane substrate 110.

An ion conductive membrane of the electrically conductive hybridmembrane is disposed between a positive electrode and a negativeelectrode of a secondary battery and the opposing surfaces are disposedfacing to each of the positive electrode and the negative electrode.Accordingly, in order that the ion conductive membrane between thepositive electrode and the negative electrode blocks moisture andselectively passes only an ion (for example, a lithium ion, etc.),regions having an ion conductivity are preferably exposed from bothsides of the ion conductive membrane.

In an alternative embodiment, with the electron conductive layer betweenthe electrically conductive hybrid membranes, two constituent elementsin the electronic device, for example, the panel and the driverintegrated circuit (IC) are configured to be connected to each other. Inthis embodiment, the electron conductive layer physically/electricallyconnects regions where the panel and the driving IC are each contacted,but other regions contacting the other electron conductive layers or therelationships with the adjacent constituent elements are preferred to beelectrically insulated.

But in the electrically conductive hybrid membrane 10 according to anembodiment, the conductive particles 120 are each exposed on the bothsides of the solid membrane substrate 110, thereby the electricallyconductive hybrid membrane 10 according to an embodiment may selectivelypass only ions and/or electrons.

According to an embodiment, the solid membrane substrate 110 maymaintain an arrangement of the conductive particles 120 in therelationship with the conductive particles 120. In this embodiment, thesolid membrane substrate 110 may have insulating properties, and mayhave a resistivity of 10 ohm-meters (Ω·m) to 10²⁵ Ω·m, e.g., 103 Ω·m to10²⁰ Ω·m. Thereby, the ion and/or electron exchange may be blocked bythe region where the solid membrane substrate 110 is formed, but ionand/or electron may be passed through the electrically conductiveparticles 120.

The solid membrane substrate 110 may have an electrical insulationproperty, so as to prevent passing ions and/or electrons in otherregions except the conductive particles 120. In addition, the solidmembrane substrate 110 may have barrier properties to gases such asmoisture, oxygen, carbon dioxide, and the like.

In an embodiment, the solid membrane substrate 110 may include thecurable material. In this embodiment, the curable material is a maincomponent for the solid membrane substrate 110. Thereby, the solidmembrane substrate 110 may strongly maintain the solid phase through thecuring process.

In an exemplary device, the solid membrane substrate 110 may be formedwith the curable material, but, optionally, may further include thevarious known organic/inorganic materials such as a polymerizationinitiator or the like while including the curable material as the maincomponent.

In an alternative exemplary device, the curable material may provide thesolid membrane substrate 110 with an appropriate level of flexibilityand also decreased possibility of defects (voids, cracks, etc.) on themembrane itself, compared to the thermoplastic material.

According to an embodiment, the curable material may include anysuitable material having a solid phase through the curing process, andthe curing method is not particularly limited. In an exemplary device,the curable material may be at least any one of a thermosettingmaterial, an ultraviolet (UV) curable material, and a moisture curablematerial. In an embodiment, the curable material may include at leasttwo materials having different curable properties of the thermosetting,ultraviolet (UV) curable, moisture curable properties.

Specific examples of the curable material may be an acryl-basedcompound, an epoxy-based compound, a urethane-based compound, aphenol-based compound, or a combination thereof.

For example, the curable material may be the acryl-based compound.

Non-limiting examples of the acryl-based compound may include at leastone type of the various cross-linking groups inside thereof in additionto an acryl group. Examples of the cross-linking group may include anisocyanate group, a diisocyanate group, a maleimide group, and the like.

In an exemplary embodiment, the curable material may have apredetermined elasticity. The elasticity may be selected depending upona temperature, and the elastic modulus at a room temperature (25° C.) ofthe solid membrane substrate 110, in which the curable material iscompletely cured to a solid phase, may be, for example, greater than orequal to about 10 MPa, greater than or equal to about 20 MPa, greaterthan or equal to about 30 MPa, greater than or equal to about 40 MPa,greater than or equal to about 50 MPa, or greater than or equal to about60 MPa, and for example, less than or equal to about 1000 MPa, less thanor equal to about 900 MPa, less than or equal to about 800 MPa, lessthan or equal to about 700 MPa, less than or equal to about 600 MPa,less than or equal to about 500 MPa, less than or equal to about 400MPa, less than or equal to about 300 MPa, less than or equal to about200 MPa, or less than or equal to about 100 MPa, or for example, about10 MPa to about 1000 MPa, about 20 MPa to about 1000 MPa, about 30 MPato about 1000 MPa, about 30 MPa to about 900 MPa, about 40 MPa to about800 MPa, about 40 MPa to about 700 MPa, about 40 MPa to about 600 MPa,about 40 MPa to about 500 MPa, about 40 MPa to about 400 MPa, about 50MPa to about 300 MPa, or about 50 MPa to about 200 MPa. When the elasticmodulus after curing the curable material satisfies the range, the solidmembrane substrate 110 may have the appropriate level of elasticity andflexibility.

In an exemplary embodiment, the elastic modulus before curing thecurable material may be selected depending upon a temperature. In anexemplary device, the curable material may have an elastic modulus at aroom temperature (25° C.) of, for example, less than or equal to about200 kPa, less than or equal to about 190 kPa, less than or equal toabout 180 kPa, less than or equal to about 170 kPa, or less than orequal to about 160 kPa, and may have an elastic modulus of, at atemperature range slightly higher than the room temperature, forexample, about 50° C. to about 200° C., for example, about 1 kPa toabout 100 kPa, or about 5 kPa to about 90 kPa. When the elastic modulusbefore curing the curable material satisfies the range, the conductiveparticles 120 which will be further described later may be easilydisposed in the membrane substrate-forming layer.

In an exemplary embodiment, the curable material may have an adhesion ortack. When the curable material further has adhesion, the conductiveparticles 120, which will be further described later, may be disposed inthe membrane substrate-forming layer including the curable material tohave a predetermined arrangement. The specific arrangement of theconductive particles 120 will be further described later. Theelectrically conductive hybrid membrane may have a tackiness of about 1Newton per square centimeter (N/cm²) to about 20 N/cm², when determinedaccording to ASTM D 3121-94 at 30° C.

In an alternative exemplary embodiment, in order that the conductiveparticles 120 are exposed each of the both surfaces of the solidmembrane substrate 110, the thickness of the solid membrane substrate110 is preferred to be at least less than or equal to a diameter of theconductive particles 120.

In an exemplary device, the solid membrane substrate 110 may have athickness which is less than or equal to about 90%, less than or equalto about 80%, less than or equal to about 70%, less than or equal toabout 60%, less than or equal to about 50%, less than or equal to about40% of the diameter of the conductive particles 120 and a thicknesswhich is at least greater than or equal to about 20%, for example,greater than or equal to about 30%. When the solid membrane substrate110 satisfies the range, the electrically conductive hybrid membrane 10may show excellent electrical conductivity, mechanical strength andbarrier properties.

In an embodiment, the conductive particles 120 may transfer ions and/orelectrons onto the both surfaces of the electrically conductive hybridmembrane 10 as mentioned above. According to this embodiment, theconductive particles 120 are exposed on the both surfaces of the solidmembrane substrate 110 to provide an electrical conductivity, so thatthe conductive particles 120 may be formed in a monolayer.

FIG. 2 is a top plane view, viewed from either side of both sides of theelectrically conductive hybrid membrane according to an embodiment.

Referring to FIG. 2 , the conductive particles 120 may be disposed inthe solid membrane substrate 110 to provide a predetermined arrangement.In an exemplary device, the conductive particles 120 may be arranged ina hexagonal form.

According to an embodiment, the predetermined arrangement may be anarrangement that the conductive particles 120 are densely disposed. Inan exemplary device, the conductive particles 120 may be arranged in ahexagonal close-packed form. In this case, the volume of conductiveparticles 120 per a unit volume is increased, so the area whereconductive particles 120 are exposed on the both sides of theelectrically conductive hybrid membrane 10 is also increased.Resultantly, it may provide an electrically conductive hybrid membrane10 with the improved electrical conductivity.

However, the specific disposition or arrangement of the conductiveparticles 120 is not limited thereto, and the arrangement or dispositionmay be varied depending upon a kind of the conductive particles 120, anapplication field of the electrically conductive hybrid membrane 10, amaterial of the curable material for the solid membrane substrate 110,and the adhesion strength (or peel strength), and the like, under theconditions that the conductive particles 120 are exposed on each theboth sides of the solid membrane substrate 110.

In an embodiment, the conductive particles 120 may include ionconductive particles, electron conductive particles, or a combinationthereof. In this embodiment, when the conductive particles 120 includeion conductive particles, the electrically conductive hybrid membrane 10may show ion conductivity; or when including the electron conductiveparticles, the electrically conductive hybrid membrane 10 may showelectron conductivity.

When the electrically conductive hybrid membrane 10 shows ionconductivity, the conductive particles 120 may conduct at least one ionof, for example, lithium ion, sodium ion, proton, potassium ion, ironion, zinc ion, magnesium ion, and potassium ion.

In an embodiment, the conductive particles 120 may show an ionconductivity to the ions of, at least, greater than or equal to about10⁻⁶ S/cm, for example, greater than or equal to about 10⁻⁵ S/cm, and,for example, less than or equal to about 1×10⁻³ S/cm or less than orequal to about 1×10⁻⁴ S/cm, or it may show an ion conductivity of, forexample, about 1×10⁻⁵ S/cm to about 1×10⁻³ S/cm, or about 1×10⁻⁴ S/cm.In this embodiment, the ranged ion conductivity may be an ionconductivity to lithium ions. However, the embodiment is not limitedthereto, but it may show excellent ion conductivity within the range tothe above-mentioned kind of ions.

In an alternative embodiment, the conductive particles 120 may include asulfide, an oxide, or a combination thereof.

In an alternative embodiment, the sulfide broadly refers to a materialformed by compounding sulfur atom with metal, oxygen, hydrocarbon, andthe like.

In an alternative embodiment, the oxide broadly refers to a materialformed by compounding oxygen atom with metal, hydrocarbon, etc. In anembodiment, examples of the oxide may be ZrO₂, AlO₃, and compoundsrepresented by Chemical Formula 1 to Chemical Formula 4. That is, theconductive particles 120 according to an embodiment may include at leastone of ZrO₂, AlO₃, and compounds represented by Chemical Formula 1 toChemical Formula 4.

Li₃La_((2/3-x))TiO₃  Chemical Formula 1

Li_(y)La₃M¹ ₂O₁₂  Chemical Formula 2

Li_((2+2z))Zn_((1−z))GeO₄  Chemical Formula 3

Li_(w)M² ₂(PO₄)₃  Chemical Formula 4

In Chemical Formula 1 to Chemical Formula 4,

M¹ is at least one element selected from zirconium (Zr), niobium (Nb),tantalum (Ta), antimony (Sb), and bismuth (Bi),

M² is at least one element selected from Aluminum (Al), germanium (Ge),titanium (Ti), hafnium (Hf), and zirconium (Zr),

0≤w≤2, 0≤x≤2/3, 5≤y≤7, and

0≤z<1.

The conductive particles 120 may use only any one of the compoundsrepresented by Chemical Formulae 1 to 4 or may use a mixture of at leasttwo of them, depending upon the kind of ion to be conducted.

In an exemplary embodiment, when the electrically conductive hybridmembrane 10 shows the electron conductivity, the conductive particles120 may include, for example, an elastomer and a metal layer formed onthe surface of the elastomer. In an exemplary device, the conductiveparticles 120 may have a core-shell structure that a metal shell layeris formed on a surface of a core made of elastomer.

The elastomer is not particularly limited as long as the material hasthe predetermined elasticity, but may include, for example, apolystyrene-based compound, an epoxy-based compound, a polyimide-basedcompound, a phenol-based compound, or a combination thereof.

The metal layer formed on the surface of the elastomer provides thepredetermined electrical conductivity to the conductive particles 120.The metal layer may be a monolayer or a multilayer of at least twolayers.

In an exemplary device, the metal included in the metal layer mayinclude, for example, gold (Au), silver (Ag), nickel (Ni), palladium(Pd), copper (Cu), or a combination thereof. The metal may be a singlemetal or an alloy of at least two of the metals.

In an exemplary embodiment, when the metal layer is a multilayer of atleast two layers, the at least two layers may include different metalsfrom each other.

In an exemplary device, the conductive particles 120 may be one that anickel layer and a gold layer are sequentially formed on a surface of anelastomer including an epoxy-based compound and a phenol-based compound.

However, an embodiment is not limited thereto, but the kind of themetal, the number of the layers, and the like may be altered in variousmanners according to the electrical conductivity required for theconductive particles 120.

A thickness of the electrically conductive hybrid membrane 10 accordingto an embodiment may be selected depending upon a thickness of the solidmembrane substrate 110 and a diameter and/or a material of theconductive particles 120, and the like, but the thickness may be, forexample, greater than or equal to about 5 μm, greater than or equal toabout 10 μm, greater than or equal to about 15 μm, greater than or equalto about 20 μm and, for example, less than or equal to about 50 μm, lessthan or equal to about 45 μm, less than or equal to about 40 μm, lessthan or equal to about 35 μm, less than or equal to about 30 μm, or lessthan or equal to about 25 μm, or for example, about 5 μm to about 50 μm,or about 20 μm to about 50 μm.

When the electrically conductive hybrid membrane 10 according to anembodiment has a thickness within the range, the flexibility and theworkability may be maintained as well as improved mechanical strengthand barrier properties provided.

As described above, the electrically conductive hybrid membrane 10according to an embodiment may pass ions and/or electrons through theconductive particles 120 exposed onto the both sides of the membrane andmay block transferring the remaining materials such as moisture, oxygen,carbon dioxide, and the like. In addition, the electrically conductivehybrid membrane 10 according to an embodiment may ensure the excellentmechanical strength and flexibility and barrier properties by defining arelationship of between a thickness of the solid membrane substrate 110and a diameter of the conductive particles 120 and may also show theexcellent electrical conductivity caused by the conductive particles120.

Hereinafter, a method of making an electrically conductive hybridmembrane according to an embodiment is described.

FIG. 3 is a flow diagram for explaining a process for an electricallyconductive hybrid membrane according to an embodiment.

A method of making an electrically conductive hybrid membrane accordingto an embodiment includes disposing the conductive particles on themembrane substrate-forming layer, pressing the membranesubstrate-forming layer and the conductive particles, and curing themembrane substrate-forming layer.

A method of making the electrically conductive hybrid membrane may besequentially performed from the left to the right in FIG. 3 .

The method of making the electrically conductive hybrid membrane mayinclude a continuous process through a conveying part and a roll. Inthis case, the lower side of the membrane substrate-forming layer may besupported by the lower release substrate. The lower release substrate isnot particularly limited as long as it may be continuously transferredor spirally wound as in the process shown in FIG. 3 , and may be apolymer substrate such as poly(ethylene terephthalate) (PET) and/orsilicon-treated PET, and the like.

In an exemplary method, the conductive particles are disposed to have apredetermined arrangement on the preliminarily prepared membranesubstrate-forming layer during disposing the conductive particles.

First, an upper release substrate covered on the upper side of themembrane substrate-forming layer is peeled off. The upper releasesubstrate may include any substrate without particular limitations aslong as it may be continuously transferred or spirally wound as in thelower release substrate, and may include a polymer substrate such as PETand/or silicon-treated PET, and the like. Second, conductive particlesare supplied onto the membrane substrate-forming layer of which theupper side is exposed. The conductive particles may be scattered, forexample, on the upper side of the membrane substrate-forming layer. Inthe process of scattering the conductive particles, the conductiveparticles may be disposed to have the predetermined arrangement asmentioned above.

According to an embodiment, the membrane substrate-forming layer mayhave an adhesion. In an exemplary device, the peel strength of themembrane substrate-forming layer during disposing the conductiveparticles before the pressing is not particularly limited, but may be atleast greater than or equal to about 0.05 N/25 mm, greater than or equalto about 0.5 N/25 mm, greater than or equal to about 1 N/25 mm, greaterthan or equal to about 2 N/25 mm, greater than or equal to about 3 N/25mm, greater than or equal to about 4 N/25 mm, or greater than or equalto about 5 N/25 mm, e.g., about 0.05 Newtons (N) per 25 millimeters (mm)to 100 N/25 mm. When the peel strength of the membrane substrate-forminglayer satisfies the range, the arranged conductive particles are notdeviated from the first arranged position but stayed.

In an exemplary embodiment, the membrane substrate-forming layer isdisposed with the conductive particles 120, so the thickness thereof maybe thicker than the initial thickness as much as the volume of thedisposed conductive particles according to Archimedes principle.Accordingly, in an embodiment, the initial thickness of the membranesubstrate-forming layer may be preliminarily prepared in a predeterminedthickness considering this point.

Specifically, when t refers to a thickness of the membranesubstrate-forming layer before disposing the conductive particles 120, Drefers to a diameter of the conductive particles 120, the t and the Dmay satisfy a relationship of Equation 1.

t≤0.4×D  Equation 1

Equation 1 may be obtained through the following calculations.

FIG. 4 is a schematic view showing the case where the electronconductive particles are disposed to have the densest structure in themembrane substrate-forming layer.

First, it is supposed that conductive particles 120, which are ideallyspherical particles having a diameter D, are arranged in an idealhexagonal close-packed form shown in FIG. 4 in the membranesubstrate-forming layer. In this case, a distance connecting centers ofthe adjacent two conductive particles is referred to as D, and a heightof a triangle connecting centers of the adjacent three conductiveparticles is √3/2×D.

When the conductive particles are arranged in N crosses and M columns,the volume of the spherical shape particles is represented by EquationA.

[N×M]×[(π/6)×D³]  Equation A

Meanwhile, the volume of the membrane substrate-forming layer afterarranging the conductive particles is represented by Equation B.

$\begin{matrix}{{\left\lbrack {N \times D} \right\rbrack \times \left\lbrack {M \times \left( \frac{\left. \sqrt{}3 \right.}{2} \right) \times D} \right\rbrack \times D} = {\left\lbrack {N \times M} \right\rbrack \times \left\lbrack {\left( \frac{\left. \sqrt{}3 \right.}{2} \right) \times D^{3}} \right\rbrack}} & {{Equation}B}\end{matrix}$

However, when t′ refers to a thickness of the membrane substrate-forminglayer after arranging the conductive particles while t refers to aninitial thickness of the membrane substrate-forming layer, arelationship of the t/t′ satisfies Equation C.

$\begin{matrix}\begin{matrix}{{t/t^{\prime}} = {\left\{ {{\left\lbrack {N \times M} \right\rbrack \times \left\lbrack {\left( \frac{\left. \sqrt{}3 \right.}{2} \right) \times D^{3}} \right\rbrack} - {\left\lbrack {N \times M} \right\rbrack \times \left\lbrack {\left( \frac{\pi}{6} \right) \times D^{3}} \right\rbrack}} \right\}/}} \\{\left\lbrack {N \times M} \right\rbrack \times \left\lbrack {\left( \frac{\left. \sqrt{}3 \right.}{2} \right) \times D^{3}} \right\rbrack} \\{= {{\left\{ \left\lbrack {\left( \frac{\left. \sqrt{}3 \right.}{2} \right) - \left( \frac{\pi}{6} \right)} \right. \right\}/\left( \frac{\left. \sqrt{}3 \right.}{2} \right)} = {\left\lbrack {1 - \left\{ {\pi/\left\{ {3 \times \left( \left( {3^{\hat{}}0.5} \right) \right.} \right\}} \right.} \right\rbrack \approx 0.4}}}\end{matrix} & {{Equation}C}\end{matrix}$

However, the thickness t′ of the membrane substrate-forming layer afterarranging the conductive particles may not be greater than the diameterD of the conductive particles, and thus in Equation C, t′ is substitutedwith D, and then Equation 1 may be provided after rearrangement of t andD.

Subsequently, the upper releasing film which was peeled off is coatedagain on the membrane substrate-forming layer arranged with theconductive particles, and then residual conductive particles which arenot arranged in the membrane substrate-forming layer are sucked usingsuction and removed. But the suction may be omitted depending upon thescattering degree of the conductive particles.

FIG. 5 is a graph showing the surface exposure of electron conductiveparticles in an electrically conductive hybrid membrane according to anembodiment, together with a relationship of the diameter of the electronconductive particles—the thickness of the membrane substrate-forminglayer before pressing.

In FIG. 5 , Li_(1.3)Al_(0.3)Ti_(1.7)(PO₄)₃ (“LATP”) particles and ZrO₂particles are used as the electron conductive particles, and anisocyanate group-containing acryl-based adhesive is used as a curablematerial, and the pressing and heating time conditions are each about 60MPa, about 150° C., and about 3 minutes, and the curing condition(ultraviolet (UV) irradiating intensity) is about 500 milliJoules persquare centimeter (mJ/cm²).

Referring to FIG. 5 , it is confirmed that the conductive particles aresunk in the solid membrane substrate, or only either one side (one sideonly) is exposed when not satisfying Equation 1. In addition, the timepoint when the both sides of the electrically conductive hybrid membraneare exposed (both side) is slightly different depending upon the kind ofthe conductive particles, but commonly it is confirmed that theconductive particles are stably exposed onto the both sides of the solidmembrane substrate from the case of satisfying Equation 1.

Subsequently, the both sides of the membrane substrate-forming layer inwhich the conductive particles are arranged are pressed using a pressingmeans.

In an embodiment, the pressing may be performed at a temperature higherthan the room temperature. Specifically, when the membranesubstrate-forming layer arranged with the conductive particles ispressed and compacted, the membrane substrate-forming layer may beheated. In an exemplary device, an optional thermal conductive metalplate (e.g., aluminum plate) is disposed on the both sides of themembrane substrate-forming layer arranged with the thermal electricallyconductive particles, and then may be pressed together with a heatingpress or the like and simultaneously, may be heated at a predeterminedtemperature.

In an exemplary embodiment with a material having a relatively highelastic modulus, the conductive particles are not exposed to each of theupper side and the lower side by only the simple pressing, and any oneside (particularly, lower side) may be covered by the solid membranesubstrate. But according to another exemplary embodiment, bysimultaneously pressing and heating the membrane substrate-forming layerarranged with the conductive particles, an elastic modulus of themembrane substrate-forming layer is slightly lowered to expose theconductive particles onto the both sides.

The elastic modulus of the pressed and heated membrane substrate-forminglayer may be changed depending upon the kind of the included curablematerial and the like, but it may show, for example, less than or equalto about 100 kPa or less than or equal to about 90 kPa at a temperatureof about 60° C. to about 250° C. This elastic modulus range is of a verylow value with respect to the elastic modulus range of the solidmembrane substrate 110.

According to an embodiment, the pressing may be performed, for example,at least greater than or equal to about 1 MPa, greater than or equal toabout 5 MPa, greater than or equal to about 10 MPa, greater than orequal to about 20 MPa, greater than or equal to about 30 MPa and mayperformed, for example, less than or equal to about 100 MPa, less thanor equal to about 90 MPa, less than or equal to about 80 MPa, or lessthan or equal to about 70 MPa, or for example, may be performed at apressure of about 1 MPa to about 100 MPa, about 5 MPa to about 100 MPa,about 10 MPa to about 100 MPa, or about 20 MPa to about 100 MPa.

When the pressing pressure during the pressing process is less thanabout 1 MPa, the conductive particles 120 may be not exposed to each ofthe upper and lower surfaces and may be unfavorably covered by the solidmembrane substrate 110; but when is greater than about 100 MPa, theconductive particles 120 is worried to be damaged.

The heating may be performed at a temperature of at least greater thanor equal to a room temperature (25° C.), for example, greater than orequal to about 50° C., greater than or equal to about 60° C., greaterthan or equal to about 70° C., or greater than or equal to about 80° C.and performed at, for example, less than or equal to about 300° C., lessthan or equal to about 250° C., or less than or equal to about 200° C.,or may be performed at, for example, about 50° C. to about 300° C.,about 50° C. to about 250° C., about 60° C. to about 250° C., about 70°C. to about 250° C., about 80° C. to about 250° C., or about 80° C. toabout 200° C.

In addition, the heating may be performed for, for example, greater thanor equal to about 10 seconds, greater than or equal to about 15 seconds,greater than or equal to about 20 seconds, greater than or equal toabout 30 seconds, or greater than or equal to about 1 minute and mayperformed for, for example, less than or equal to about 10 minutes, lessthan or equal to about 9 minutes, less than or equal to about 8 minutes,or less than or equal to about 7 minutes, or may be performed for, forexample, about 15 seconds to about 10 minutes, about 30 seconds to about10 minutes, about 1 minute to about 10 minutes, about 1 minute to about9 minutes, about 1 minute to about 8 minutes, or about 1 minute to about7 minutes.

When the heating temperature and/or time are insufficient, it may bedifficult to lower the elastic modulus of the membrane substrate-forminglayer as much as the conductive particles 120 are inserted, so theconductive particles 120 may not be exposed on each of the upper sideand the lower side of the membrane as it may be covered with the solidmembrane substrate 110; but if the heating temperature is too much, themembrane substrate-forming layer and/or the conductive particles 120 maybe damaged.

When the pressing and heating are completed, the pressed membranesubstrate-forming layer is cured using a curing means. The curing meansincludes an ultraviolet (UV) curing means, a thermal curing means, amoisture curing means, or a combination thereof, and may include atleast one kind of the curing means according to the curable property ofthe curable material included in the membrane substrate-forming layer.

Subsequently, when the curing is completed, the upper release substrateand the lower release substrate are each peeled off to provide anelectrically conductive hybrid membrane 10 according to an embodiment.The order of peeling the upper release substrate and the lower releasesubstrate is not limited in an embodiment, and they may besimultaneously peeled off.

In an exemplary embodiment, the obtained electrically conductive hybridmembrane 10 has excellent mechanical strength and flexibility, so it maybe spirally wound using a spiral-wound roll after peeling off theupper/lower release substrates.

As described above, the method of making an electrically conductivehybrid membrane according to an embodiment does not require to satisfyatmosphere conditions such as vacuum, so it is easy to control theoverall process conditions compared to a wet process, and also theelectrically conductive hybrid membrane may be fabricated through thecontinuous process, so the mass productivity is also excellent.

Hereinafter, a secondary battery including the electrically conductivehybrid membrane according to an embodiment is described.

FIG. 6 is a schematic view showing a secondary battery including anelectrically conductive hybrid membrane according to an embodiment.

Referring to FIG. 6 , a secondary battery 1 according to an embodimentincludes a positive electrode 11, a negative electrode 12, and anelectrically conductive hybrid membrane 10 between the positiveelectrode 11 and the negative electrode 12.

First, a negative electrode 12 is prepared.

The negative electrode 12 may use a lithium metal thin film or mayinclude a current collector and a negative active material layerdisposed on the current collector. In an exemplary embodiment, thenegative electrode 12 may be used in a state that the lithium metal thinfilm is disposed on a conductive substrate which is a current collector.The lithium metal thin film may be integrated with the currentcollector.

In the negative electrode 12, the current collector may be one selectedfrom the group consisting from stainless steel, copper, nickel, iron,and cobalt, but is not necessarily limited thereto and may include anymetallic substrate as long as it has good conductivity and being useablein the field pertained to the art. For example, the current collectormay be a conductive oxide substrate, a conductive polymer substrate, andthe like. In addition, the current collector may have the variousstructures such as a shape of which a conductive metal, a conductivemetal oxide, or a conductive polymer is coated on one surface of theinsulating substrate, besides a structure that the entire substrate ismade of a conductivity material. The current collector may be a flexiblesubstrate. Thus, the current collector may be easily bent. In addition,after bending this, the current collector may be easily recovered to theoriginal shape.

In addition, the negative electrode 12 may further include othernegative active materials in addition to the lithium metal. The negativeelectrode 12 may include an alloy of lithium metal and other negativeactive materials, a composite of lithium metal and other negative activematerials, or a mixture of lithium metal and other negative activematerials.

Other negative active materials that may be added in the negativeelectrode 12 may be, for example, at least one selected from the groupconsisting of a metal capable of being alloyed with lithium, transitionmetal oxide, non-transition metal oxide, and a carbon-based material.

In an exemplary embodiment, the metal capable of being alloyed withlithium may be Si, Sn, Al, Ge, Pb, Bi, Sb, a Si—Y alloy (wherein Y is anelement selected from an alkali metal, an alkaline-earth metal, a Group13 element, a Group 14 element, a transition metal, a rare earthelement, or a combination thereof element, and not Si), a Sn—Y alloy(wherein Y is an element selected from an alkali metal, analkaline-earth metal, a Group 13 element, a Group 14 element, atransition metal, a rare earth element, or a combination thereof, andnot Sn), and the like. The element, Y may be Mg, Ca, Sr, Ba, Ra, Sc, Y,Ti, Zr, Hf, Rf, V, Nb, Ta, db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru,Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge,P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.

In an exemplary device, the transition metal oxide may be lithiumtitanium oxide, vanadium oxide, lithium vanadium oxide, and the like.

In another exemplary device, the non-transition metal oxide may be SnO₂,SiO_(x) (0<x<2), and the like.

The carbon-based material may be crystalline carbon, amorphous carbon,or a mixture thereof. The crystalline carbon may be graphite such asamorphous, sheet-shaped, flake shaped, spherical shaped or fiber-shapednatural graphite or artificial graphite, and the amorphous carbon may besoft carbon (carbon fired at low temperature) or hard carbon, mesophasepitch carbonate, fired cokes, and the like.

Alternatively, the negative electrode 12 may include other negativeactive material instead of lithium metal. The negative electrode 12 maybe obtained using a negative active material composition including thenegative active material instead of the lithium metal, a conductiveagent, a binder, and a solvent.

In an exemplary method, after preparing the negative active materialcomposition, it is directly coated on a current collector to provide anegative electrode plate, or it is casted on a separate support, and thenegative active material film detached from the support is laminated onthe current collector to provide a negative electrode plate. Thenegative electrode is not limited to the mentioned shapes but mayinclude any other shapes used in the fields pertaining to the art. In anexemplary method, the negative electrode may be obtained by furtherprinting a negative active material ink including the negative activematerial, an electrolyte solution, and the like on a current collectoraccording to an inkjet.

The negative active material may be in the form of a powder. The powderynegative active material may be employed for a negative active materialcomposition or a negative active material ink.

The conductive agent may include carbon black, graphite particulate, andthe like, but is not limited thereto, and may include any one as long asit is used as a conductive agent in the field pertained to the art.

The binder may include a vinylidene fluoride/hexafluoropropylenecopolymer, polyvinylidene fluoride (“PVDF”), polyacrylonitrile,polymethylmethacrylate, polytetrafluoroethylene and a mixture thereof,or a styrene butadiene rubber-based polymer, and the like, but is notlimited thereto, and may include any one as long as it is used as abinder in the field pertaining to the art.

The solvent may include N-methylpyrrolidone, acetone or water and thelike, but is not limited thereto, and may include any one as long as itis used in the field pertaining to the art.

The amounts of the negative active material, the conductive agent, thebinder, and the solvent are as used level for the secondary battery,particularly, the lithium secondary battery. At least one of theconductive agent, the binder, and the solvent may be omitted accordingto the usage and the structure of the secondary battery.

Next, the positive electrode 11 may be fabricated as follows.

The positive electrode 11 may be obtained in accordance with the sameprocedure as in the negative active material composition, except that apositive active material is used instead of the negative activematerial.

In the positive active material composition, a conductive agent, abinder, and a solvent may be the same as in the negative active materialcomposition. The positive active material, the conductive agent, thebinder, and the solvent are mixed to provide the positive activematerial composition. The positive active material composition isdirectly coated on an aluminum current collector and dried to provide apositive electrode plate formed with a positive active material layer.Alternatively, the positive active material composition is casted on aseparate support, and then a film obtained by being detached from thesupport is laminated on the aluminum current collector to provide apositive electrode plate formed with the positive active material layer.

The positive active material may be a lithium-containing metal oxide andmay be any material in the related art without limitation. In anexemplary embodiment, the positive active material may be a compositeoxide of a metal selected from cobalt, manganese, nickel, and acombination thereof and lithium and specific examples thereof may be oneof compounds represented by Li_(a)A_(1-b)B_(b)D₂ (wherein, in thechemical formula, 0.90≤a≤1.8 and 0≤b≤0.5); Li_(a)E_(1-b)BbO_(2-c)D_(c)(wherein, in the chemical formula, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05);LiE_(2-b)B_(b)O_(4-c)D_(c) (wherein, in the chemical formula, 0≤b≤0.5,0≤c≤0.05); Li_(a)Ni_(1-b-c)CO_(b)B_(c)D_(α) (wherein, in the chemicalformula, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2);Li_(a)Ni_(1-b-c)Co_(b)B_(c)O_(2-α)F_(α) (wherein, in the chemicalformula, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2);Li_(a)Ni_(1-b-c)CO_(b)B_(c)O_(2-α)F₂ (wherein, in the chemical formula,0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li_(a)Ni_(1-b-c)Mn_(b)B_(c)D_(α)(wherein, in the chemical formula, 0.90≤a≤1.8, 0:5≤b≤0.5, 0≤c≤0.05,0<α≤2); Li_(a)Ni_(1-b-c)Mn_(b)B_(c)O_(2-α)F_(α) (wherein, in thechemical formula, 0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2);Li_(a)Ni_(1-b-c)Mn_(b)B_(c)O_(2-α)F₂ (wherein, in the chemical formula,0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li_(a)Ni_(b)E_(c)G_(d)O₂(wherein, in the chemical formula, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5,0.001≤d≤0.1); Li_(a)Ni_(b)Co_(c)Mn_(d)GeO₂ (wherein, in the chemicalformula, 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1);Li_(a)NiG_(b)O₂ (wherein, in the chemical formula, 0.90≤a≤1.8,0.001≤b≤0.1); Li_(a)CoG_(b)O₂ (wherein, in the chemical formula,0.90≤a≤1.8, 0.001≤b≤0.1); Li_(a)MnG_(b)O₂ (wherein, in the chemicalformula, 0.90≤a≤1.8, 0.001≤b≤0.1); Li_(a)Mn₂GbO₄ (wherein, in thechemical formula, 0.90≤a≤1.8, 0.001≤b≤0.1); QO₂; QS₂; LiQS₂; V₂O₅;LiV₂O₅; LiIO₂; LiNiVO₄; Li_((3-f))J₂(PO₄)₃ (0≤f≤2); Li_((3-f)) Fe₂(PO₄)₃(0≤f≤2); and LiFePO₄:

In the above chemical formulae, A is Ni, Co, Mn, or a combinationthereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element,or a combination thereof; D is O, F, S, P, or a combination thereof; Eis Co, Mn, or a combination thereof; F is F, S. P, or a combinationthereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combinationthereof; Q is Ti, Mo, Mn, or a combination thereof; I is Cr, V, Fe, Sc,Y, or a combination thereof; and J is V, Cr, Mn, Co, Ni, Cu, or acombination thereof.

In an exemplary embodiment, the positive active material may be LiCoO₂,LiMn_(x)O_(2x) (x=1, 2), LiNi_(1-x)Mn_(x)O_(2x) (0<x<1),Ni_(1-x-y)Co_(x)Mn_(y)O₂ (O≤x≤0.5, 0≤y≤0.5), LiFePO₄, and the like.

The compounds may have a coating layer on the surface, or may be mixedwith another compound having a coating layer. The coating layer mayinclude at least one coating element compound of an oxide of a coatingelement, a hydroxide of a coating element, an oxyhydroxide of a coatingelement, an oxycarbonate of a coating element, or a hydroxyl carbonateof a coating element. The compound for the coating layer may beamorphous or crystalline. The coating element included in the coatinglayer may include Mg, Al, Co, K, Na, Ca. Si, Ti, V, Sn, Ge, Ga, B, As,Zr, or a mixture thereof. The coating layer may be disposed in a methodhaving no adverse influence on properties of a positive active materialby using these elements in the compound. An exemplary method may includeany coating method such as spray coating, dipping, and the like, but isnot illustrated in more detail since it is well-known in the relatedfield.

The amounts of the positive active material, the conductive agent, thebinder, and the solvent are as used level for the secondary battery,particularly, the lithium secondary battery.

Next, the aforementioned electrically conductive hybrid membrane 10 isprepared. The structure of the electrically conductive hybrid membrane10 is same as in above, and may be interposed between the negativeelectrode 12 and the positive electrode 11 to block a material exception and to selectively pass ion.

As described above, the secondary battery 1, according to an embodiment,may be an all-solid-state battery that the aforementioned electricallyconductive hybrid membrane 10 is used as a separator and/or aseparator-cum-electrolyte. That is, even in the case that theelectrically conductive hybrid membrane 10 according to an embodiment isused as a separator for the all-solid-state battery, the secondarybattery 1 may have excellent electrochemical characteristics asdescribed above.

In addition, the secondary battery 1, according to an embodiment, hasexcellent ion conductivity caused by the aforementioned electricallyconductive hybrid membrane 10, and also shows improved efficiency andlife-span by minimizing the side reaction of the electrode.

Hereinafter, an electronic device including the electrically conductivehybrid membrane according to an embodiment is described.

FIG. 7 is a schematic view illustrating an electronic device includingan electrically conductive hybrid membrane according to an embodiment.

Referring to FIG. 7 , the electronic device 2 according to an embodimentphysically and electrically connects the display panel 21 to the driverIC 22.

The display panel 21 may at least include an array substrate including athin film transistor and an opposing substrate configured to oppose thearray substrate. When the display panel 21 is a liquid crystal displaypanel, a liquid crystal layer may be interposed between the arraysubstrate and the opposing substrate. Alternatively, when the displaypanel 21 is an organic light emitting display panel, an organic lightemitting diode may be interposed between the array substrate and theopposing substrate.

The driver IC 22 is connected with a pad formed in a peripheral area ofthe array substrate and responses a control signal applied through anexternal device to output a driving signal for driving the arraysubstrate.

As described above, the electronic device 2, according to an embodiment,may be a display device using the electrically conductive hybridmembrane 10 as an anisotropic conductive film. In other words, theelectrically conductive hybrid membrane 10 according to an embodimenthas excellent electron conductivity, so that it is easily utilized as ananisotropic conductive film electrically connecting constituent elementsin the display device.

Hereinafter, the making the electrically conductive hybrid membraneaccording to an embodiment and properties of the obtained electricallyconductive hybrid membrane are illustrated in more detail with referenceto examples. However, these examples are exemplary, and the presentscope is not limited thereto.

EXAMPLES Manufacture of Electrically Conductive Hybrid MembraneAccording to Example 1 and Comparative Examples 1 to 3 and Evaluation ofElectron Conductivity Example 1

As conductive particles, electron conductive particles (Sekisui ChemicalCo., Ltd., AU-250) having a diameter of about 50 μm (49.5 μm to 50.5 μm)in which a nickel layer and a gold layer are sequentially formed(thickness of nickel layer+thickness of gold layer=0.22 μm) on a surfaceof an elastomer core including an epoxy-based compound and aphenol-based compound are used. A membrane substrate-forming layer isprepared by mixing a curable material of an acryl-based adhesiveincluding a diisocyanate group (Tosoh Corporation, Coronate L45E) and aphotopolymerization initiator of 1-hydroxy-cyclohexyl-phenyl-ketone(BASF, Irgacure 184). A releasing film (silicon-treated PET film) iscoated on each of the upper/lower sides of the membranesubstrate-forming layer. The membrane substrate-forming layer has aninitial thickness of 15 μm.

Subsequently, the release film covering the upper side of the membranesubstrate-forming layer is peeled off, and then the electron conductiveparticles are scattered on the upper side of the membranesubstrate-forming layer in an area of 20 mm×20 mm. After the scattering,the peeled release film is coated on the upper side of the membranesubstrate-forming layer again.

Then the adhesion film on which particles are scattered is disposedbetween two aluminum plates having a thickness of 4 mm, and heated andpressed under the conditions of 60 MPa and 150° C. for 3 minutes using ahydraulic heating press (Carver). Subsequently, the heated and pressedsamples are taken out and cooled down to a room temperature (25° C.),and irradiated with ultraviolet (UV) by a UV radiator (Heraeus, FusionUV Light Hammer) (radiation dose: 2000 mJ/cm²) to cure a membranesubstrate-forming layer.

Then the release films covering the upper/lower sides of the sample arepeeled off to provide an electrically conductive hybrid membraneaccording to Example 1.

Comparative Example 1

An electrically conductive hybrid membrane according to ComparativeExample 1 is manufactured in accordance with the same procedure as inExample 1, except that the initial thickness of the membranesubstrate-forming layer is changed to 50 μm.

Comparative Example 2

An electrically conductive hybrid membrane according to ComparativeExample 2 is manufactured in accordance with the same procedure as inExample 1, except that the initial thickness of the membranesubstrate-forming layer is changed to 30 μm.

Comparative Example 3

An electrically conductive hybrid membrane according to ComparativeExample 3 is manufactured in accordance with the same procedure as inExample 1, except that the conductive particles are not coated.

The central regions of the electrically conductive hybrid membranesobtained from Example 1 and Comparative Examples 1 to 3 are each cutinto 10 mm×10 mm and then are measured for an electrical resistance(mega ohm, MΩ) of the sample using the ohm meter.

Each specification of Example 1 and Comparative Examples 1 to 3 and theresistance results thereof are shown in Table 1.

TABLE 1 Comparative Comparative Comparative Example 1 Example 1 Example2 Example 3 Electrically Material Elastomer Elastomer Elastomer Notinclude conductive core/nickel core/nickel core/nickel particlelayer/gold layer/gold layer/gold layer layer layer Diameter [D] 50 (μm)50 (μm) 50 (μm) — Initial thickness of membrane 15 (μm) 50 (μm) 30 (μm)15 (μm) substrate-forming layer [t] [t]/[D] 0.3 1.0 0.6 ∞ Elastic BeforeRoom 150 (kPa) 150 (kPa) 150 (kPa) 150 (kPa) modulus of UV temperaturemembrane irradiation Heating 5 (kPa) 5 (kPa) 5 (kPa) 5 (kPa) substrate-After Room 70 (MPa) 70 (MPa) 70 (MPa) 70 (MPa) forming UV temperaturelayer irradiation Evaluation Electrical 0.78 (Ω) unmeasurableunmeasurable unmeasurable Result Resistance

Referring to Table 1, Example 1, which satisfies Equation 1 representingthe relationship between the initial thickness t of the membranesubstrate-forming layer and a diameter D of the electrically conductiveparticles, shows electrical conductivity, but Comparative Examples 1 to3 are unmeasurable for the electrical conductivity.

Specifically, as Comparative Example 3 does not include the conductiveparticles, itself, it does not show electrical conductivity; and asComparative Examples 1 and 2 have the relationship of t/d of greaterthan 0.4, the conductive particles are not exposed on both sides of thesolid membrane substrate.

Also, considering that the electrical resistance of the aluminum foilhaving a thickness of 30 μm is 0.37Ω, it is understood that theelectrically conductive hybrid membrane according to Example 1 shows theexcellent electrical conductivity similar to the aluminum foil.

Manufacture of Electrically Conductive Hybrid Membrane according toExamples 2 to 3 and Comparative Examples 4 to 5 and Evaluation of IonConductivity Example 2

An electrically conductive hybrid membrane according to Example 2 ismanufactured in accordance with the same procedure as in Example 1,except that for the conductive particles, LATP particles having adiameter of about 33 μm (28 μm to 33 μm) are filtered by a sieve, andthe initial thickness of the membrane substrate-forming layer is changedto 15 μm, the pressing and heating conditions are changed into 60 MPa,130° C., and 3 minutes, and the ultraviolet (UV) radiation dose ischanged to 500 mJ/cm².

Example 3

An electrically conductive hybrid membrane according to Example 3 ismanufactured in accordance with the same procedure as in Example 2,except that a thermosetting acryl-based adhesive (TOAGOSEI, AronixUVP-1211) which is heating cross-linkable at a temperature of 100° C. orhigher according to a photodimerization of maleimide is used as amaterial for forming a membrane substrate-forming layer (initialthickness: 15 μm), and the irradiating ultraviolet (UV) is omitted.

Comparative Example 4

An electrically conductive hybrid membrane according to ComparativeExample 4 is manufactured in accordance with the same procedure as inExample 2, except that a thermoplastic resin of polyvinylidene chloride(“PVDC,” Asahi Kasei, Saran Wrap) (initial thickness: 10 μm) is used asa material for forming a membrane substrate-forming layer and heated at150° C. for 3 minutes without pressing the same.

Comparative Example 5

The LATP particles disclosed in Example 2 are scattered on awater-soluble adhesive tape, and then a cycloolefin polymer (COP) (JapanZeon, ZEONOR 1060R)-containing solution is coated thereon and dried at90° C. for 20 minutes, which are repeated for 5 times forming a membranesubstrate-forming layer. The initial thickness of the membranesubstrate-forming layer was 10 μm. Subsequently, the surface of themembrane is etched with an etching solution, and the LATP particles areexposed on both sides of the cycloolefin polymer film, and thenwater-soluble adhesive tape is peeled off to provide an electricallyconductive hybrid membrane according to Comparative Example 5.

The upper sides and the lower sides of the electrically conductivehybrid membranes according to Examples 2 to 3 and Comparative Examples 4to 5 are each taken an image by SEM, and it is monitored whether voidsare generated.

Also, during the process of making the electrically conductive hybridmembrane, the peel strength of the membrane substrate-forming layer andthe release film after scattering particles is measured under theconditions of 25° C., 180° C., and 300 mm/minute.

Also, for the electrically conductive hybrid membrane, a Warburgimpedance is measured according to an AC impedance method to evaluate alithium ion conductivity.

Table 2 show the summary of specifications of Examples 2 and 3 andComparative Examples 4 and 5, the void generation in the membranesubstrate, the peel strength of the membrane substrate-forming layer,and the lithium ion conductivity.

TABLE 2 Comparative Comparative Example 2 Example 3 Example 4 Example 5Conductive Material LATP LATP LATP LATP particle Diameter 33 (μm) 33(μm) 33 (μm) 33 (μm) Material of membrane Acryl-based Acryl-based PVDCCOP substrate-forming compound compound layer Material ultravioletthermosetting thermoplastic thermoplastic characteristics (UV) curableProcessing manner pressing, heating, heating, heating coating andheating heating etching Peel strength 20 (N/25 mm) 5 (N/25 mm) 0.01(N/25 mm) 10 (N/25 mm) or (upon scattering less particles) ElasticBefore 150 (kPa) 90 (kPa) 2 (GPa) 3 (GPa) modulus processing After 70(MPa) 80 (MPa) 2 (GPa) 3 (GPa) processing Void generation No No Yes NoLithium ion ◯ ◯ X (short circuit) ◯ conductivity

Referring to Table 2, it is confirmed that Examples 2 and 3 having themembrane substrate-forming layer using the curable material showexcellent lithium ion conductivity and do not show the void generation,compared to Comparative Examples 4 and 5 having the membranesubstrate-forming layer using the thermoplastic material. Thereby, it isconfirmed that Examples 2 and 3 show higher stability and massproducibility than in Comparative Examples 4 and 5.

FIG. 8 is a SEM image showing the lower surface of the electricallyconductive hybrid membrane according to Comparative Example 4.

Referring to FIG. 8 , when the membrane substrate-forming layer isformed using the thermoplastic resin as in Comparative Example 4, theconductive particles are inappropriately inserted into the membranesubstrate-forming composition due to the excessively high elasticmodulus, so that the conductive particles are not properly exposed ontothe lower surface, and also lots of the voids are generated on the lowersurface as shown in FIG. 8 .

Manufacture of Electrically Conductive Hybrid Membrane According toExamples 4 to 7 and Comparative Examples 6 to 8 and Evaluation ofRelated Properties Example 4

An electrically conductive hybrid membrane according to Example 4 ismanufactured in accordance with the same procedure as in Example 1,except that the initial thickness of the membrane substrate-forminglayer is changed to 15 μm, and the pressing and heating conditions arechanged to 60 MPa, 130° C., and 3 minutes, and the ultraviolet (UV) doseis changed to 500 mJ/cm².

Example 5

An electrically conductive hybrid membrane according to Example 5 ismanufactured in accordance with the same procedure as in Example 1,except that one-component curable epoxy adhesion (thermosetting,manufactured by Cemedine, EP138) (initial thickness: 15 μm) is used as amaterial for forming a membrane substrate, and the irradiatingultraviolet (UV) is omitted.

Example 6

A moisture curable one-component adhesion (Cemedine, UM700) including amain component of a prepolymer having a terminal NCO group as a materialfor forming a membrane substrate is coated on a release film in athickness of about 10 μm according to a blade coating method. Theelectrically conductive particles which are used in Example 1 arescattered onto a 20 mm×20 mm area of the coated adhesion, and thenpressed without heating at 60 MPa, 23° C., for 120 minutes using ahydraulic heating press used in Example 1. Then the release film coatedon the particle-scattered surface is peeled off and allowed to stand for60 minutes to absorb moisture, and then the reminded release film isalso peeled off and allowed to stand for 60 minutes to absorb moisture,so as to provide an electrically conductive hybrid membrane according toExample 6.

Example 7

As a material for a membrane substrate-forming layer, a modifiedphenol-based adhesion (thermosetting, manufactured by Cemedine, Cemedine110) is coated as a wet film on a release film in a thickness of about20 μm and naturally dried at 23° C. for 3 hours to provide a membranesubstrate-forming layer having a film thickness of 10 μm. Then theelectrically conductive particles used in Example 1 are scattered onto a20 mm×20 mm area of the coated adhesion, and the release film is coatedon the scattered surface and heated and pressed at 60 MPa, at 180° C.for 30 minutes using the hydraulic heating press which is used inExample 1, and the release films are peeled off to provide anelectrically conductive hybrid membrane according to Example 7.

Comparative Example 6

An electrically conductive hybrid membrane according to ComparativeExample 6 is manufactured in accordance with the same procedure as inExample 1, except that the thermoplastic resin of PVDC which is used inComparative Example 4 as a material for a membrane substrate-forminglayer is used, and the irradiating ultraviolet (UV) is omitted.

Comparative Example 7

An electrically conductive hybrid membrane according to ComparativeExample 7 is manufactured in accordance with the same procedure as inExample 1, except that the thermoplastic resin of COP which is used inComparative Example 5 as a material for a membrane substrate-forminglayer is used, the pressing and heating conditions are changed into 60MPa, 260° C. for 5 minutes, and the irradiating ultraviolet (UV) isomitted.

Comparative Example 8

An electrically conductive hybrid membrane according to ComparativeExample 8 is manufactured in accordance with the same procedure as inExample 1, except that the polypropylene (TORAY, TORAYFAN, 2500H, 30 μm)(initial thickness: 30 μm) is used as a material for a membranesubstrate-forming layer, the pressing and heating conditions are changedinto 60 MPa, 170° C. for 5 minutes, and the irradiating ultraviolet (UV)is omitted

The electrically conductive hybrid membranes according to Examples 4 10to 7 and Comparative Examples 6 to 8 are measured for the voidgeneration in the membrane substrate, the peel strength of the membranesubstrate-forming layer, and the electrical resistance according to thesame procedure as in above.

In addition, the SEM images are measured for the upper/lower sides ofthe electrically conductive hybrid membrane, and observed whether theelectrically conductive particles are exposed on the both surfaces ofthe solid membrane substrate.

Additionally, the electrically conductive hybrid membrane is performedwith the flexibility evaluation using a cylindrical mandrel methodaccording to JIS.K. 5600-5-1. Specifically, the bend test is performedusing a mandrel having a diameter of 5 mm, which is repeated for 10times, and it is determined whether cracks and/or damages occur on thesurface of the bend test-completed conductive hybrid membrane.

In this case, “∘” indicates a case that the cracks and/or damages arenot found on the surface of the conductive hybrid membrane; and “X”indicates a case that the cracks and/or damages occur or a case that thebend testis impossible to perform.

Every specification and every property measurement result of Examples 4to 7 and Comparative Examples 6 to 8 are summarized and shown in Table3.

TABLE 3 Comp. Comp. Comp. Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 6 Ex. 7 Ex. 8Material of Acryl- Epoxy- Urethane- Phenol- PVDC COP PP membrane basedbased based based substrate- compound compound compound compound forminglayer Material UV Thermosetting Moisture Thermosetting ThermoplasticThermoplastic Thermoplastic characteristic curable curable Processingheating, heating, room heating, heating, heating, heating, mannerpressing pressing temperature, pressing pressing pressing pressingpressing Peel 20 (N/ 75 (N/ 5 (N/ 50 (N/ less than less than less thanstrength 25 mm) 25 mm) 25 mm) 25 mm) 0.01 (N/ 0.01 (N/ 0.01 (N/ (upon 25mm) 25 mm) 25 mm) scattering particles) Void No No No No Yes Yes YesParticle Exposed Exposed Exposed Exposed Exposed Exposed Exposedexposure on both on both on both on both on one on one on one sidessides sides sides side side side Flexibility ◯ ◯ ◯ ◯ ◯ X X (unbendable)(stripes generation) Electrical 0.80(Ω) 1.50(Ω) 2.00(Ω) 2.50(Ω)Unmeasurable unmeasurable unmeasurable resistance

Referring to Table 3, Examples using the curable material have higherpeel strength of the membrane substrate-forming layer and are moreflexible than in Comparative Examples using the thermoplastic material,and as the electrically conductive particles are exposed on both sidesof the solid membrane substrate to provide an electrical conductivity(electron conductivity).

In Comparative Examples, it is confirmed that the peel strength of themembrane substrate-forming layer is also low, a plurality of voids occuron the surface of the membrane substrate, and the electricalconductivity is also not shown as the conductive particles are notexposed on both sides of the membrane substrate.

Manufacture of Electrically Conductive Hybrid Membrane According toExamples 8 to 12 and Comparative Examples 9 to 13 and Evaluation ofProperties Example 8

An electrically conductive hybrid membrane according to Example 8 ismanufactured in accordance with the same procedure as in Example 1,except that the LATP particles, which are used in Example 2, are used asthe conductive particles, the acryl-based adhesive, which is used inExample 1, is used as the material for forming the membrane-forminglayer (initial thickness: 8 μm), and the pressing and heating conditionsand the ultraviolet (UV) dose are changed.

Example 9

An electrically conductive hybrid membrane according to Example 9 ismanufactured in accordance with the same procedure as in Example 1,except that ZrO₂ particles having a diameter of about 50 μm are used asthe conductive particle, and the pressing and heating conditions arechanged.

Example 10

An electrically conductive hybrid membrane according to Example 10 ismanufactured in accordance with the same procedure as in Example 1,except that the pressing and heating conditions and the ultraviolet (UV)irradiating dose are changed.

Example 11

An electrically conductive hybrid membrane according to Example 11 ismanufactured in accordance with the same procedure as in Example 1,except that an acryl-based adhesive having a weight of the diisocyanategroup in 1.3 times with respect to the acryl-based adhesive used inExample 1, and the pressing and heating conditions and the ultraviolet(UV) irradiating dose are changed.

Example 12

An electrically conductive hybrid membrane according to Example 12 ismanufactured in accordance with the same procedure as in Example 1,except that an acryl-based adhesive, which is used in Example 3, is usedas the material for the membrane-forming layer, and the pressing andheating conditions are changed.

Comparative Example 9

An electrically conductive hybrid membrane according to ComparativeExample 9 is manufactured in accordance with the same procedure as inExample 9, except that the pressing and heating conditions are changed.

Comparative Example 10

An electrically conductive hybrid membrane according to ComparativeExample 10 is manufactured in accordance with the same procedure as inExample 8, except that the acryl-based adhesive, which is used inExample 3, is used as a material for a membrane-forming layer, and thepressing and heating conditions and the ultraviolet (UV) irradiatingdose are changed.

Comparative Example 11

An electrically conductive hybrid membrane according to ComparativeExample 11 is manufactured in accordance with the same procedure as inExample 8, except that the pressing and heating conditions are changed,and the irradiating ultraviolet (UV) is omitted.

Comparative Example 12

An electrically conductive hybrid membrane according to ComparativeExample 12 is manufactured in accordance with the same procedure as inExample 10, except that the material for the membrane-forming layer, thepressing and heating conditions, and the ultraviolet (UV) radiation doseare changed.

As a material for forming a membrane-forming layer, an acryl-basedadhesive of which a weight-based cross-linking density of the polymermain chain is 0.7 times with respect to the acryl-based adhesive whichis used in Example 1, and a maleimide weight is 1.3 times with respectto the acryl-base adhesive which is used in Example 3, the cross-linkingproperty is higher after the UV curing than the acryl-based adhesivewhich is used in Example 3 while the cross-linking density is low beforethe UV curing.

Comparative Example 13

An electrically conductive hybrid membrane according to ComparativeExample 13 is manufactured in accordance with the same procedure as inExample 12, except that the pressing and heating conditions and theultraviolet (UV) irradiating dose are changed.

For Examples 8 to 12 and Comparative Examples 9 to 13, the exposure ofthe conductive particles, the flexibility, and the electricalresistance, and the peel strength before pressing and heating themembrane-substrate forming layer are evaluated in accordance with thesame procedure as in the above.

Every specification of Examples 8 to 12 and Comparative Examples 9 to 13and the property results are summarized and shown in Table 4.

TABLE 4 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Initial thickness of membrane 8(μm) 15 (μm) 15 (μm) 15 (μm) 15 (μm) forming layer [t] ElectricallyMaterial LATP ZrO₂ elastomer elastomer elastomer conductive core/nickelcore/nickel core/nickel particles layer/gold layer/gold layer/gold layerlayer layer Diameter [D] 33 (μm) 50 (μm) 50 (μm) 50 (μm) 50 (μm) [t]/[D]0.24 0.30 0.30 0.30 0.30 Peel strength (before heating) 20 (N/25 5 (N/2520 (N/25 75 (N/25 10 (N/25 mm) mm) mm) mm) mm) Heating, Pressure 60(MPa) 60 (MPa) 60 (MPa) 60 (MPa) 60 (MPa) pressing Time 3 (minutes) 3(minutes) 3 (minutes) 3 (minutes) 3 (minutes) Temperature 102-108 (° C.)150-154 (° C.) 102-108 (° C.) 150-154 (° C.) 100-110 (° C.) Ultraviolet(UV) radiation dose 500 (mJ/cm²) 2000 (mJ/cm²) 500 (mJ/cm²) 500 (mJ/cm²)2000 (mJ/cm²) Elastic Before Room 90 (kPa) 150 (kPa) 90 (kPa) 300 (kPa)400 (kPa) modulus UV temperature irradiation Upon 70 (kPa) 1 (kPa) 70(kPa) 50 (kPa) 12 (kPa) pressing After curing 100 (MPa) 70 (MPa) 100(MPa) 120 (MPa) 700 (MPa) (room temperature) Particle exposure ExposedExposed Exposed Exposed Exposed on both on both on both on both on bothsides sides sides sides sides Membrane status ◯ ◯ ◯ ◯ ◯ Electricalresistance — — 0.80 (Ω) 1.50 (Ω) 2.00 (Ω) Comp. Comp. Comp. Comp. Comp.Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Initial thickness of membrane 15 (μm)8 (μm) 8 (μm) 15 (μm) 15 (μm) forming layer [t] Electrically MaterialZrO₂ LATP LATP elastomer elastomer conductive core/nickel core/nickelparticles layer/gold layer/gold layer layer Diameter [D] 50 (μm) 33 (μm)33 (μm) 50 (μm) 50 (μm) [t]/[D] 0.30 0.24 0.24 0.30 0.30 Peel strength(before heating) 5 (N/25 5 (N/25 20 (N/25 20 (N/25 5 (N/25 mm) mm) mm)mm) mm) Heating, Pressure 60 (MPa) 60 (MPa) 60 (MPa) 60 (MPa) 60 (MPa)pressing Time 3 (minutes) 3 (minutes) 3 (minutes) 3 (minutes) 3(minutes) Temperature 25 (° C.) 50-60 (° C.) 50-60 (° C.) 25 (° C.)50-60 (° C.) Ultraviolet (UV) radiation dose 2000 (mJ/cm²) 2000 (mJ/cm²)— 2000 (mJ/cm²) 2000 (mJ/cm²) Elastic Before Room 150 (kPa) 500 (kPa) 90(kPa) 150 (kPa) 90 (kPa) modulus UV temperature irradiation Upon 150(kPa) 30 (kPa) 70 (kPa) 150 (kPa) 70 (kPa) pressing After curing 70(MPa) 5000 (MPa) 0.07 (MPa) 70 (MPa) 5000 (MPa) (room temperature)Particle exposure Exposed Exposed Exposed Exposed Exposed on both onboth on both on one on both sides sides sides side sides Membrane status◯ X X ◯ X (crack (insufficient (crack generation) membrane generation)strength) Electrical resistance — — — unmeasurable unmeasurable(overload)

Referring to Table 4, it is confirmed that in Examples in which thematerial for forming a membrane-forming layer is controlled to have anelastic modulus of less than or equal to about 100 kPa during thepressing and heating process, the conductive particles are easilyexposed on the both sides of the solid membrane substrate, and theexcellent electron conductivity (in cases of Examples 10 to 12) isshown, and the excellent elastic modulus is shown at a room temperature(25° C.), even after the curing. In addition, it is confirmed that theresults are obtained by using either an electron conductive particle oran ion conductive particle as the as the conductive particle.

Manufacture of Electrically Conductive Hybrid Membrane According toExample 13 and Comparative Example 14 and Evaluation of SurfaceCharacteristics and Electric Characteristics Example 13

An electrically conductive hybrid membrane according to Example 13 ismanufactured in accordance with the same procedure as in Example 1,except that a curable acryl-based adhesive (TOAGOSEI, Aronix UVP-1301)is used as a material for a membrane-forming layer, and the pressing andheating conditions and the ultraviolet (UV) radiation dose are changed.

Comparative Example 14

An electrically conductive hybrid membrane according to ComparativeExample 14 is manufactured in accordance with the same procedure as inExample 13, except that the pressing and heating conditions are changed.

The upper side and the lower side of the electrically conductive hybridmembrane according to Example 13 and Comparative Example 14 are eachobserved by SEM, and the results are shown in FIGS. 9 to 12 .

In addition, the electrical resistance of each electrically conductivehybrid membranes according to Example 13 and Comparative Example 14 isevaluated in accordance with the same procedure as in above.

Every specification of Example 13 and Comparative Example 14, and theproperty results are summarized and shown in Table 5.

TABLE 5 Example 13 Comparative Example 14 Electrically Elastomercore/nickel Elastomer core/nickel conductive particle layer/gold layerlayer/gold layer Membrane-forming Acryl-based compound Acryl-basedcompound layer material Membrane-forming 15 (μm) 15 (μm) layer materialinitial thickness Heating, Pressure 60 (MPa) 0 (MPa) pressing Time 5(min) 5 (min) Temperature 136-141 (° C.) 134-146 (° C.) Electricalresistance 0.78(Ω) 2.37(Ω)

FIGS. 9 and 10 are SEM images showing the upper side (FIG. 9 ) and thelower side (FIG. 10 ) of the electrically conductive hybrid membraneaccording to Example 13; and FIGS. 11 and 12 are SEM images showing theupper side (FIG. 11 ) and the lower side (FIG. 12 ) of the electricallyconductive hybrid membrane according to Comparative Example 14.

Referring to Table 5 and FIGS. 9 to 12 , it is also confirmed that theelectrically conductive hybrid membrane according to Example 13 showsthe excellent electrical conductivity, and also the electricallyconductive particles are regularly exposed on both upper and lowersides, and the electrically conductive particles form a predetermineddense arrangement

In Example 13, it is understood that the electrically conductiveparticles on the upper side are more protruded than on the lower side inComparative Example 14, and also a ratio of the electrically conductiveparticles exposed on the lower side is lower than in other Examples.Thereby, it is confirmed that Example 13 shows lower resistance thanComparative Example 14.

Accordingly, from Experimental Examples, it is confirmed that theelectrically conductive hybrid membrane according to an embodiment showsexcellent electrical conductivity and excellent mechanical strength,excellent flexibility, and excellent barrier properties or the like.

While this disclosure has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments. On the contrary, it is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

What is claimed is:
 1. A hybrid membrane, comprising: a solid membranesubstrate comprising a cured product of an adhesive material; and aconductive particle comprising an ion conductive particle, an electronconductive particle, or a combination thereof, the conductive particlebeing exposed from both opposing surfaces of the solid membranesubstrate, wherein a thickness t of the solid membrane substrate and adiameter D of the conductive particle satisfy the relationship ofEquation 1:t≤0.4×D.  Equation 1
 2. The hybrid membrane of claim 1, wherein thesolid membrane substrate is an insulating substrate.
 3. The hybridmembrane of claim 1, wherein a resistivity of the solid membranesubstrate is 10 ohm-meters to 10²⁵ ohm-meters.
 4. The hybrid membrane ofclaim 1, wherein an elastic modulus of the solid membrane substrate is10 megaPascals to 1000 megaPascals at room temperature.
 5. The hybridmembrane of claim 1, wherein a peel strength of the solid membranesubstrate is 0.05 Newton per 25 millimeters to 100 Newtons per 25millimeters.
 6. The hybrid membrane of claim 1, wherein the adhesivematerial comprises a thermosetting adhesive material, an ultraviolet(UV) curable adhesive material, a moisture curable adhesive material, ora combination thereof.
 7. The hybrid membrane of claim 6, wherein theadhesive material comprises an acryl adhesive, an epoxy adhesive, aurethane adhesive, a phenol adhesive, or a combination thereof.
 8. Thehybrid membrane of claim 1, wherein a tackiness of the adhesive materialis 1 Newton per square centimeter to 20 Newtons per square centimeter.9. The hybrid membrane of claim 1, wherein the conductive particles arearranged in hexagonal shape.
 10. The hybrid membrane of claim 1, whereinthe ion conductive particle conducts at least one ion of a lithium ion,a sodium ion, a proton, an iron ion, a zinc ion, a magnesium ion, and apotassium ion.
 11. The hybrid membrane of claim 1, wherein an ionconductivity of the ion conductive particle is 1×10⁻⁵ Siemens percentimeter to 1×10⁻³ Siemens per centimeter.
 12. The hybrid membrane ofclaim 1, wherein the electron conductive particle comprises an elastomerand a metal layer disposed on the surface of the elastomer.
 13. Thehybrid membrane of claim 12, wherein the elastomer comprises apolystyrene compound, an epoxy compound, a polyimide compound, a phenolcompound, or a combination thereof, and the metal layer comprises gold(Au), silver (Ag), nickel (Ni), palladium (Pd), copper (Cu), or acombination thereof.
 14. The hybrid membrane of claim 1, wherein thethickness t of the solid membrane substrate and the diameter D of theconductive particle satisfy the relationship: 0.24×D≤t≤0.30×D.
 15. Anelectronic device comprising the hybrid membrane of claim
 1. 16. Asecondary battery comprising a positive electrode; a negative electrode;and the hybrid membrane disposed between the positive electrode and thenegative electrode, wherein the hybrid membrane comprises a solidmembrane substrate comprising a cured product of an adhesive material;and an ionic conductive particle, the ionic conductive particle beingexposed from both opposing surfaces of the solid membrane substrate, andwherein a thickness t of the solid membrane substrate and a diameter Dof the ionic conductive particle satisfy the relationship of Equation 1:t≤0.4×D.  Equation 1
 17. An anisotropic conductive film comprising asolid membrane substrate comprising a cured product of an adhesivematerial; and an electron conductive particle, the electron conductiveparticle being exposed from both opposing surfaces of the solid membranesubstrate, wherein a thickness t of the solid membrane substrate and adiameter D of the electron conductive particle satisfy the relationshipof Equation 1:t≤0.4×D.  Equation 1
 18. An electronic device comprising the anisotropicconductive film of claim 17.